US3952000A - Biocidal bicyclic polyoxymethyleneoxazolidines - Google Patents
Biocidal bicyclic polyoxymethyleneoxazolidines Download PDFInfo
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- US3952000A US3952000A US05/519,885 US51988574A US3952000A US 3952000 A US3952000 A US 3952000A US 51988574 A US51988574 A US 51988574A US 3952000 A US3952000 A US 3952000A
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- hydroxymethyl
- biocidal
- dioxabicyclo
- aza
- polyoxymethyleneoxazolidines
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
- C07D263/04—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
- C09D5/024—Emulsion paints including aerosols characterised by the additives
- C09D5/025—Preservatives, e.g. antimicrobial agents
Definitions
- This invention relates to a certain bicyclic polyoxymethyleneoxazolidines. It further relates to biocidal compositions that are aqueous solutions which contain from 20 to 80 percent by weight of these bicyclic polyoxymethyleneoxazolidines and which are useful in controlling the growth of bacteria and fungi in aqueous surface-coating compositions.
- paints and varnishes often have inadequate resistance to the action of microorganisms.
- Some of these coating compositions sucn as enamels and house paints, contain as their resinous binders drying oils, oleoresinous varnishes, or alkyd resins, which are subject to attack by fungi and bacteria.
- Others for example, aqueous dispersions of water-insoluble synthetic linear polymers, generally contain as plasticizers and thickeners materials that have their origin in animal or vegetable sources and that render the compositions susceptible to mildew. The resulting deterioration of the surface-coating compositions seriously hinders their full scale utilization, particularly in those areas and in those applications that are conducive to such attack.
- biocidal materials have been suggested for use in surface-coating compositions, but none has proven entirely satisfactory in this application. Some do not provide the required prolonged protection against attack by microorganisms, while others undergo sulfide staining and still others hydrolyze in alkaline aqueous paint systems or separate from the applied coating by migration, volatilization, or leaching after the coating has been spread in a thin layer over the surface to be protected. Some biocidal materials cause the coating compositions to gel or impart color or odor to them.
- This invention relates to biocides that are of particular value in surface-coating compositions.
- biocides which are stable in aqueous solutions, which are thoroughly compatible with the resinous binders that commonly are used in surface-coating compositions, and which are resistant to sulfide staining, provide excellent and prolonged resistance to deterioration resulting from attack by bacteria, fungi, and other microorganisms without adversely affecting the color, pH, viscosity, and other physical properties of the surface-coating compositions.
- biocidal compounds of this invention have the structural formula ##EQU2## wherein each R represents hydrogen, alkyl of 1 to 6 carbon atoms, phenyl, halophenyl, or --(CH 2 O) m CH 2 OH; m represents a number in the range of 0 to 2; and n! represents a number in the range of 1 to 4.
- polyoxymethyleneoxazolidines are the following: 5-[hydroxymethyl-di(oxymethylene)]-1-aza-3,7-dioxabicyclo(3.3.0)octane, 5-[hydroxymethyl-tri(oxymethylene)]-1-aza-3,7-dioxabicyclo(3.3.0)octane, 2-phenyl-5-[hydroxymethyl-tetra(oxymethylene)]-1-aza-3,7-dioxabicyclo(3.3.0)octane, 2,8-bis( ⁇ -chloroethyl)-5-[hydroxymethyl-penta(oxymethylene)]-1-aza-3,7-dioxabicyclo(3.3.0)octane, 2,8-bis(p-chlorophenyl)-5-[hydroxymethyl-tri(oxymethylene)]-1-aza-3,7-dioxabicyclo(3.3.0)octane, 2-hydroxymethyl-5-[hydroxymethyl-[hydroxymethyl-[
- the preferred compounds for use in surface-coating compositions are those in which the total number of oxymethylene (--CH 2 O--) units in one or more of the substituents on the oxazolidine ring is not greater than six. While compounds having more than six oxymethylene units in their ring substituents are very effective in controlling the growth of bacteria and fungi, they tend to be somewhat unstable in surface-coating compositions and to impart to them the odor of formaldehyde. Examples of the preferred bicyclic compounds include polyoxymethyleneoxazolidines in which
- the substituent in the 5-position is --(CH 2 O(CH 2 O) 1-4 -CH 2 OH and the substituents in the 2- and 8-positions are hydrogen, alkyl, phenyl, or halophenyl;
- the substituent in the 5-position is --CH 2 OCH 2 OCH 2 OH, that in the 2-position is --(CH 2 O) 0-2 CH 2 OH, and that in the 8-position is hydrogen, alkyl, phenyl, or halophenyl; and
- the substituent in the 5-position is --CH 2 O(CH 2 O) 1-2 -CH 2 OH and the substituents in the 2- and 8-positions are --CH 2 OH.
- biocidal compounds of this invention may be prepared by any suitable and convenient procedure.
- they may be prepared by the reaction of the appropriate oxazolidine with formaldehyde and/or paraformaldehyde.
- they may be prepared by the reaction of an aminoalcohol with formaldehyde and/or paraformaldehyde and optionally another aldehyde. These reactions are ordinarily carried out in aqueous solution at a temperature between about 20° and 100°C.
- the reactions are preferably carried out at ambient temperature; when paraformaldehyde or a mixture of aqueous formaldehyde and paraformaldehyde is used, it is preferred that the reaction be carried out at a higher temperature.
- aminoalcohols that can be reacted with formaldehyde and, if desired, another aldehyde to form the novel polyoxymethyleneoxazolidines is tris(hydroxymethyl)aminomethane.
- the aminoalcohol is reacted with formaldehyde or a mixture of formaldehyde and a second aldehyde.
- the second aldehyde may be an aliphatic aldehyde, such as acetaldehyde, ⁇ -chloracetaldehyde, propionaldehyde, butyraldehyde, or 2-ethylbutyraldehyde; an aromatic aldehyde, such as benzaldehyde, p-chlorobenzaldehyde, or 2,4-dichlorobenzaldehyde; a dialdehyde, such as glyoxal, succinaldehyde, or glutaraldehyde; or a mixture of these aldehydes.
- an aromatic aldehyde such as benzaldehyde, p-chlorobenzaldehyde, or 2,4-dichlorobenzaldehyde
- a dialdehyde such as glyoxal, succinaldehyde, or glutaraldehyde; or a mixture of these aldehydes.
- reaction products may be recovered from the aqueous solutions in which they are formed and purified by known techniques. In most cases the products are mixtures comprising polyoxymethyleneoxazolidines having the structural formula set forth hereinbefore.
- the aqueous solutions which contain 20 percent to 80 percent and preferably 40 percent to 60 percent by weight of one or more of the aforementioned polyoxymethyleneoxazolidines, provide better biocidal activity for a given concentration of the polyoxymethyleneoxazolidine in the surface-coating composition.
- the surface-coating compositions to which the aqueous polyoxymethyleneoxazolidine solutions have been added tend to become lighter in color on aging.
- polyoxymethyleneoxazolidines of this invention can be used to impart bacterial and fungal resistance to a wide variety of surface-coating compositions including both water-based and organic solvent-based coating systems.
- the polyoxymethyleneoxazolidines are preferably used as the biocide in aqueous surface-coating compositions that contain about 10 percent to 60 percent by weight of a water-insoluble, film-forming, resinous binder that is an oleoresinous binder, a synthetic linear addition polymer, or a mixture of these binders.
- the useful aqueous dispersions of synthetic linear addition polymers are ordinarily prepared by the emulsion polymerization of ethylenically-unsaturated monomers.
- polymers polyvinyl acetate; polyvinyl butyrate; polyvinyl chloride; copolymers of vinyl acetate with vinyl chloride or acrylonitrile; copolymers of vinyl chloride with vinylidene chloride; polyethylene; polyisobutylene; polystyrene; copolymers of styrene with maleic anhydride or butadiene; copolymers of acrylonitrile with butadiene; copolymers of methacrylic acid esters of alcohols having 1 to 8 carbon atoms with vinyl acetate, vinyl chloride, acrylonitrile, or styrene; copolymers of acrylic acid esters of alcohols having 1 to 8 carbon atoms with vinyl acetate, vinyl chloride, acrylonitrile, or styrene; and mixtures thereof.
- Suitable oleoresinous binders including drying oils, such as linseed oil, tung oil, soybean oil, dehydrated castor oil, safflower oil, or fish oil; bodied drying oils; blends of drying oils or bodied drying oils with a resin component such as limed rosin, an ester gum, or phenolic resin; oleoresinous varnishes formed by heating one of the aforementioned resins with one or more drying oils or bodied drying oils; alkyd resins, which are resinous products resulting from the reaction of a polyhydric alcohol, such as pentaerythritol or glycerol, with a dicarboxylic acid, such as phthalic anhydride, and fatty acids; and mixtures thereof.
- drying oils such as linseed oil, tung oil, soybean oil, dehydrated castor oil, safflower oil, or fish oil
- bodied drying oils blends of drying oils or bodied drying oils with a resin component such as limed rosin
- polyoxymethyleneoxazolidines can also be used as the biocide in organic solvent-based systems that contain an oleoresinous binder as hereinbefore defined.
- biocidal compounds of this invention will bring about an appreciable improvement in the resistance of the composition to attack by fungi and bacteria. Three percent or more of the biocidal compounds can be used, but these larger amounts ordinarily do not provide further improvement in the properties of the surface-coating compositions and for this reason are not usually used.
- the amount of the biocidal compound that will provide optimum protection for a surface-coating composition depends upon such factors as the choice of the biocidal compound, the choice of resinous binder and other ingredients of the composition and the amount of each of these materials that is used, and the application for which the coating composition is intended.
- polyoxymethyleneoxazolidine 1 percent to 2 percent is used to protect surface-coating compositions from attack by fungi. From 0.1 percent to 0.5 percent of a polyoxymethyleneoxazolidine, based on the weight of the composition, is preferably incorporated into aqueous surface-coating compositions to protect them from attack by bacteria.
- the surface-coating compositions may contain various auxiliary materials, such as pigments, extenders, solvents, dyes, defoaming agents, driers, thickeners, emulsifiers, plasticizers, other biocides, and the like in the amounts ordinarily used for these purposes.
- auxiliary materials such as pigments, extenders, solvents, dyes, defoaming agents, driers, thickeners, emulsifiers, plasticizers, other biocides, and the like in the amounts ordinarily used for these purposes.
- the biocidal compounds may be incorporated into the surface-coating compositions by any suitable procedure. As has been indicated hereinbefore, the best results are obtained when aqueous solutions of the polyoxymethyleneoxazolidines are added to aqueous surface-coating compositions.
- the biocidal compounds can be combined with the pigments and other components to form a pigment phase that is mixed with the resinous binder and water or organic solvent to form the surface-coating composition.
- the product was shown by NMR, IR, and GC analysis of its silyl ethers to be a mixture containing about 20% of 5-hydroxymethyl-1-aza-3,7-dioxabicyclo(3.3.0)octane, 37% of 5-hydroxymethoxymethyl-1-aza-3,7-dioxabicyclo(3.3.0)octane, 14% of 5-[hydroxymethyl-di(oxymethylene)]-1-aza-3,7-dioxabicyclo-(3.3.0)octane, 21% of 5-[hydroxymethyl-tri(oxymethylene)]-1-aza-3,7-dioxabicyclo(3.3.0)octane, and 8% of 5-[hydroxymethyl-tetra-(oxymethylene)]-1-aza-3,7-dioxabicyclo(3.3.0)octane.
- a polyvinyl acetate latex paint was prepared by mixing together the following materials:
- This paint had the following properties as determined by standard paint testing procedures:
- An acrylic latex paint was prepared by mixing together the following materials:
- This paint had the following properties:
- An exterior house paint was prepared by mixing together the following materials:
- the polyvinyl acetate latex paint, the acrylic latex paint, and the oil-based paint were evaluated by means of an agar diffusion assay.
- agar is inoculated with the test organism, the treated paint is placed in a well cut from the agar, and after incubation at 28°C. and 85-95% relative humidity, the activity of the biocide is measured by zones of inhibition.
- the biocidal compounds tested and the results obtained are given in the table that follows. In this table
- Examples 1 and 2 which are mixtures of substituted oxazolidines that contain the comparator 5-hydroxymethyl-1-aza-3,7-dioxabicyclo(3.3.0)octane as well as the 5-hydroxymethylpolyoxymethylene-1-aza-3,7-dioxabicyclo(3.3.0)octanes of this invention, were substantially more effective against bacteria and fungi than the comparator.
- the product of Example 3 is more active at the 0.5% level in the PVA paint and at the 1% level in the acrylic paint than the comparator at the 2% level.
- Each of the other bicyclic polyoxymethyleneoxazolidines disclosed herein can be used in a similar way to protect surface-coating compositions from attack by bacteria and fungi.
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Abstract
Biocidal compositions useful in controlling the growth of bacteria and fungi in aqueous surface coatings are aqueous solutions that contain from 20 percent to 80 percent by weight of a bicyclic polyoxymethyleneoxazolidine having the structural formula CH2O(CH2O)nCH2OH ¦ CH2--C---CH2 ¦¦¦ ONO ANGLE ANGLE CHCH ¦¦ RR wherein each R represents hydrogen, alkyl of 1 to 6 carbon atoms, phenyl, halophenyl, or -(CH2O)mCH2OH; m represents a number in the range of 0 to 2; and n represents a number in the range of 1 to 4.
Description
This is a division of our copending application Ser. No. 447,797, which was filed on Mar. 4, 1974 and which is now U.S. Pat. No. 3,890,264.
This invention relates to a certain bicyclic polyoxymethyleneoxazolidines. It further relates to biocidal compositions that are aqueous solutions which contain from 20 to 80 percent by weight of these bicyclic polyoxymethyleneoxazolidines and which are useful in controlling the growth of bacteria and fungi in aqueous surface-coating compositions.
It is well known in the art that paints and varnishes often have inadequate resistance to the action of microorganisms. Some of these coating compositions, sucn as enamels and house paints, contain as their resinous binders drying oils, oleoresinous varnishes, or alkyd resins, which are subject to attack by fungi and bacteria. Others, for example, aqueous dispersions of water-insoluble synthetic linear polymers, generally contain as plasticizers and thickeners materials that have their origin in animal or vegetable sources and that render the compositions susceptible to mildew. The resulting deterioration of the surface-coating compositions seriously hinders their full scale utilization, particularly in those areas and in those applications that are conducive to such attack.
Various biocidal materials have been suggested for use in surface-coating compositions, but none has proven entirely satisfactory in this application. Some do not provide the required prolonged protection against attack by microorganisms, while others undergo sulfide staining and still others hydrolyze in alkaline aqueous paint systems or separate from the applied coating by migration, volatilization, or leaching after the coating has been spread in a thin layer over the surface to be protected. Some biocidal materials cause the coating compositions to gel or impart color or odor to them.
This invention relates to biocides that are of particular value in surface-coating compositions. These biocides, which are stable in aqueous solutions, which are thoroughly compatible with the resinous binders that commonly are used in surface-coating compositions, and which are resistant to sulfide staining, provide excellent and prolonged resistance to deterioration resulting from attack by bacteria, fungi, and other microorganisms without adversely affecting the color, pH, viscosity, and other physical properties of the surface-coating compositions.
The biocidal compounds of this invention have the structural formula ##EQU2## wherein each R represents hydrogen, alkyl of 1 to 6 carbon atoms, phenyl, halophenyl, or --(CH2 O)m CH2 OH; m represents a number in the range of 0 to 2; and n! represents a number in the range of 1 to 4.
Illustrative of these polyoxymethyleneoxazolidines are the following: 5-[hydroxymethyl-di(oxymethylene)]-1-aza-3,7-dioxabicyclo(3.3.0)octane, 5-[hydroxymethyl-tri(oxymethylene)]-1-aza-3,7-dioxabicyclo(3.3.0)octane, 2-phenyl-5-[hydroxymethyl-tetra(oxymethylene)]-1-aza-3,7-dioxabicyclo(3.3.0)octane, 2,8-bis(α-chloroethyl)-5-[hydroxymethyl-penta(oxymethylene)]-1-aza-3,7-dioxabicyclo(3.3.0)octane, 2,8-bis(p-chlorophenyl)-5-[hydroxymethyl-tri(oxymethylene)]-1-aza-3,7-dioxabicyclo(3.3.0)octane, 2-hydroxymethyl-5-[hydroxymethyl-tetra(oxymethylene)]-1-aza-3,7-dioxabicyclo(3.3.0)octane, 2,8-bis(2-ethylbutyl)-5-[hydroxymethyl-tri(oxymethylene)]-1-aza-3,7-dioxabicyclo(3.3.0)octane, and 2,8-bis(hydroxymethyl-5-[hydroxymethyl-di)oxymethylene)]-1-aza-3,7-dioxabicyclo(3.3.0)octane.
The preferred compounds for use in surface-coating compositions are those in which the total number of oxymethylene (--CH2 O--) units in one or more of the substituents on the oxazolidine ring is not greater than six. While compounds having more than six oxymethylene units in their ring substituents are very effective in controlling the growth of bacteria and fungi, they tend to be somewhat unstable in surface-coating compositions and to impart to them the odor of formaldehyde. Examples of the preferred bicyclic compounds include polyoxymethyleneoxazolidines in which
i. the substituent in the 5-position is --(CH2 O(CH2 O)1-4 -CH2 OH and the substituents in the 2- and 8-positions are hydrogen, alkyl, phenyl, or halophenyl;
ii. the substituent in the 5-position is --CH2 OCH2 OCH2 OH, that in the 2-position is --(CH2 O)0-2 CH2 OH, and that in the 8-position is hydrogen, alkyl, phenyl, or halophenyl; and
iii. the substituent in the 5-position is --CH2 O(CH2 O)1-2 -CH2 OH and the substituents in the 2- and 8-positions are --CH2 OH.
The biocidal compounds of this invention may be prepared by any suitable and convenient procedure. For example, they may be prepared by the reaction of the appropriate oxazolidine with formaldehyde and/or paraformaldehyde. Alternatively, they may be prepared by the reaction of an aminoalcohol with formaldehyde and/or paraformaldehyde and optionally another aldehyde. These reactions are ordinarily carried out in aqueous solution at a temperature between about 20° and 100°C. When an aqueous formaldehyde solution is used, the reactions are preferably carried out at ambient temperature; when paraformaldehyde or a mixture of aqueous formaldehyde and paraformaldehyde is used, it is preferred that the reaction be carried out at a higher temperature.
Among the aminoalcohols that can be reacted with formaldehyde and, if desired, another aldehyde to form the novel polyoxymethyleneoxazolidines is tris(hydroxymethyl)aminomethane. The aminoalcohol is reacted with formaldehyde or a mixture of formaldehyde and a second aldehyde. The second aldehyde may be an aliphatic aldehyde, such as acetaldehyde, α-chloracetaldehyde, propionaldehyde, butyraldehyde, or 2-ethylbutyraldehyde; an aromatic aldehyde, such as benzaldehyde, p-chlorobenzaldehyde, or 2,4-dichlorobenzaldehyde; a dialdehyde, such as glyoxal, succinaldehyde, or glutaraldehyde; or a mixture of these aldehydes.
The reaction products may be recovered from the aqueous solutions in which they are formed and purified by known techniques. In most cases the products are mixtures comprising polyoxymethyleneoxazolidines having the structural formula set forth hereinbefore.
Particularly advantageous results have been obtained when the aqueous solutions of polyoxymethyleneoxazolidines resulting from the reactions previously described are used without separation or purification of the biocidal compound or additional treatment other than adjustment of the concentration of the biocidal component to the desired level to protect suface-coating compositions from attack by bacteria and fungi. In addition to costing less than the purified polyoxymethyleneoxazolidines and being easier to incorporate into aqueous surface-coating compositions, the aqueous solutions, which contain 20 percent to 80 percent and preferably 40 percent to 60 percent by weight of one or more of the aforementioned polyoxymethyleneoxazolidines, provide better biocidal activity for a given concentration of the polyoxymethyleneoxazolidine in the surface-coating composition. Unlike most other aqueous surface-coating compositions that contain a biocide, the surface-coating compositions to which the aqueous polyoxymethyleneoxazolidine solutions have been added tend to become lighter in color on aging.
The polyoxymethyleneoxazolidines of this invention can be used to impart bacterial and fungal resistance to a wide variety of surface-coating compositions including both water-based and organic solvent-based coating systems.
The polyoxymethyleneoxazolidines are preferably used as the biocide in aqueous surface-coating compositions that contain about 10 percent to 60 percent by weight of a water-insoluble, film-forming, resinous binder that is an oleoresinous binder, a synthetic linear addition polymer, or a mixture of these binders. The useful aqueous dispersions of synthetic linear addition polymers are ordinarily prepared by the emulsion polymerization of ethylenically-unsaturated monomers. Illustrative of these polymers are polyvinyl acetate; polyvinyl butyrate; polyvinyl chloride; copolymers of vinyl acetate with vinyl chloride or acrylonitrile; copolymers of vinyl chloride with vinylidene chloride; polyethylene; polyisobutylene; polystyrene; copolymers of styrene with maleic anhydride or butadiene; copolymers of acrylonitrile with butadiene; copolymers of methacrylic acid esters of alcohols having 1 to 8 carbon atoms with vinyl acetate, vinyl chloride, acrylonitrile, or styrene; copolymers of acrylic acid esters of alcohols having 1 to 8 carbon atoms with vinyl acetate, vinyl chloride, acrylonitrile, or styrene; and mixtures thereof. Suitable oleoresinous binders including drying oils, such as linseed oil, tung oil, soybean oil, dehydrated castor oil, safflower oil, or fish oil; bodied drying oils; blends of drying oils or bodied drying oils with a resin component such as limed rosin, an ester gum, or phenolic resin; oleoresinous varnishes formed by heating one of the aforementioned resins with one or more drying oils or bodied drying oils; alkyd resins, which are resinous products resulting from the reaction of a polyhydric alcohol, such as pentaerythritol or glycerol, with a dicarboxylic acid, such as phthalic anhydride, and fatty acids; and mixtures thereof.
The polyoxymethyleneoxazolidines can also be used as the biocide in organic solvent-based systems that contain an oleoresinous binder as hereinbefore defined.
The addition to surface-coating compositions of as little as 0.1 percent by weight of one or more of the biocidal compounds of this invention will bring about an appreciable improvement in the resistance of the composition to attack by fungi and bacteria. Three percent or more of the biocidal compounds can be used, but these larger amounts ordinarily do not provide further improvement in the properties of the surface-coating compositions and for this reason are not usually used. The amount of the biocidal compound that will provide optimum protection for a surface-coating composition depends upon such factors as the choice of the biocidal compound, the choice of resinous binder and other ingredients of the composition and the amount of each of these materials that is used, and the application for which the coating composition is intended. In most cases 1 percent to 2 percent of polyoxymethyleneoxazolidine, based on the weight of the composition, is used to protect surface-coating compositions from attack by fungi. From 0.1 percent to 0.5 percent of a polyoxymethyleneoxazolidine, based on the weight of the composition, is preferably incorporated into aqueous surface-coating compositions to protect them from attack by bacteria.
In addition to the resinous binder and the biocidal compound, the surface-coating compositions may contain various auxiliary materials, such as pigments, extenders, solvents, dyes, defoaming agents, driers, thickeners, emulsifiers, plasticizers, other biocides, and the like in the amounts ordinarily used for these purposes.
The biocidal compounds may be incorporated into the surface-coating compositions by any suitable procedure. As has been indicated hereinbefore, the best results are obtained when aqueous solutions of the polyoxymethyleneoxazolidines are added to aqueous surface-coating compositions. Alternatively, the biocidal compounds can be combined with the pigments and other components to form a pigment phase that is mixed with the resinous binder and water or organic solvent to form the surface-coating composition.
The invention is further illustrated by the following examples.
A mixture of 60.5 grams (0.5 mole) of tris(hydroxymethyl)aminomethane, 121.5 grams (1.5 moles) of 37% aqueous formaldehyde solution, and 31.6 grams (1.0 mole) of 95% paraformaldehyde was stirred and heated at its reflux temperature until a homogeneous solution was obtained. The solution was cooled and filtered. There was obtained 213 grams of a clear yellow solution that contained 43.1% of water and 56.9% of solids. The pH of an 0.1 M solution of the product was 6.6. The product was shown by NMR, IR, and GC analysis of its silyl ethers to be a mixture of 5-hydroxymethyl-1-aza-3,7-dioxabicyclo(3.3.0)octane, 5-hydroxymethoxymethyl-1-aza-3,7-dioxabicyclo(3.3.0)octane, and 5-hydroxymethylpolyoxymethylene-1-aza-3,7-dioxabicyclo(3.3.0)octanes having the structural formula ##EQU3## wherein x represents numbers in the range of 1 to 3.
A mixture of 60.5 grams (0.5 mole) of tris(hydroxymethyl)aminomethane, 121.5 grams (1.5 moles) of 37% aqueous formaldehyde solution, and 47.3 grams (1.5 moles) of 95% paraformaldehyde was stirred and heated at its reflux temperature until a homogeneous solution was obtained. The solution was cooled and filtered. There was obtained 229.3 grams of a clear yellow solution that contained 40.1% of water and 59.9% of solids. The pH of an 0.1 M solution of the product was 6.6. The product was shown by NMR, IR, and GC analysis of its silyl ethers to be a mixture containing about 20% of 5-hydroxymethyl-1-aza-3,7-dioxabicyclo(3.3.0)octane, 37% of 5-hydroxymethoxymethyl-1-aza-3,7-dioxabicyclo(3.3.0)octane, 14% of 5-[hydroxymethyl-di(oxymethylene)]-1-aza-3,7-dioxabicyclo-(3.3.0)octane, 21% of 5-[hydroxymethyl-tri(oxymethylene)]-1-aza-3,7-dioxabicyclo(3.3.0)octane, and 8% of 5-[hydroxymethyl-tetra-(oxymethylene)]-1-aza-3,7-dioxabicyclo(3.3.0)octane.
A mixture of 29.0 grams (0.2 mole) of 5-hydroxymethyl-1-aza-3,7-dioxabicyclo(3.3.0)octane and 32.4 grams (0.4 mole) of 37% aqueous formaldehyde solution was stirred at ambient temperature until a homogeneous solution was obtained. The product was an aqueous solution that contained 26.1% of water 73.9% of 5-[hydroxymethyl-di(oxymethylene)]-1-aza-3,7-dioxabicyclo(3.3.0)-octane. The pH of an 0.1 M solution of the product was 6.9.
A. A polyvinyl acetate latex paint was prepared by mixing together the following materials:
Parts by Weight
______________________________________
Water 481.5
25% Aqueous solution of sodium salt of
24
maleic anhydride/diisobutylene copolymer
Potassium pyrophosphate 3
Long chain fatty acid alkanolamide
9
Defoamer 6
Ethylene glycol 75
11/4 % Aqueous solution of hydroxy-
375
ethylcellulose
Aqueous emulsion containing 55% of poly-
1299
vinyl acetate
Diethyl ether of diethylene glycol
30
Titanium dioxide 690
Talc 345
Calcium metasilicate 150
______________________________________
This paint had the following properties as determined by standard paint testing procedures:
Viscosity 65 K.U. Brookfield Viscosity 800 cps. (No. 4 spindle, 60 rpm) pH 7.8 Yellowness Index 3.0
Small amounts of the biocidal compounds of this invention or comparative biocides were added to portions of this paint.
B. An acrylic latex paint was prepared by mixing together the following materials:
Parts by Weight
______________________________________
Water 168
Alkyl aryl ether surfactant
6
25% Aqueous solution of sodium salt of
27
maleic anhydride/diisobutylene copolymer
Defoamer 12
2% Aqueous solution of hydroxyethyl-
300
cellulose
Ethylene glycol 60
Titanium dioxide 750
Mica (waterground) 90
Calcium carbonate 375
Ammonium hydroxide (28%) 6
Aqueous dispersion containing 46% acrylic
1642
ester copolymer (66% ethyl acrylate,
32.5% methyl acrylate, and 1.5% acrylic acid)
______________________________________
This paint had the following properties:
Viscosity 72 K.U.
Brookfield Viscosity (No. 3
1250
spindle, 60 rpm) (cps)
Yellowness index 2.6
pH 9.2
Small amounts of the biocidal compounds of this invention or comparative biocides were added to portions of this paint.
C. An exterior house paint was prepared by mixing together the following materials:
Parts by Weight
______________________________________
Basic lead carbonate
288
Zinc oxide 232
Titanium dioxide (rutile)
149
Talc 260
Linseed oil 242
Bodied linseed oil 114
Mineral spirits 114
Antiskinning agent 2
Manganese naphthenate (6%)
2.27
Lead naphthenate (24%)
11.3
______________________________________
Small amounts of the biocidal compounds of this invention or comparative biocides were added to portions of this paint.
D. The polyvinyl acetate latex paint, the acrylic latex paint, and the oil-based paint were evaluated by means of an agar diffusion assay. In this test, agar is inoculated with the test organism, the treated paint is placed in a well cut from the agar, and after incubation at 28°C. and 85-95% relative humidity, the activity of the biocide is measured by zones of inhibition. The biocidal compounds tested and the results obtained are given in the table that follows. In this table
ZO = Zone of inhibited growth in mm.
O = No zone of inhibition; no growth
Tr = Trace zone of inhibited growth
-- = Not tested
Bacteria A
-- Mixed paint spoilage strains
B -- Pseudomonas aeruginosa
C -- Aerobacter aerogenes
Fungi D -- Pullularia pullulans
E -- Penicillium crustosum
F -- Aspergillus niger
Table
__________________________________________________________________________
Activity of Polyoxymethyleneoxazolidines
as Biocides in Paints
Test Biocidal Activity
Level
Effect on Liquid Paint
Bacteria Fungi
Biocide Paint
(%) pH Odor
Color
Viscosity
A B C D E F
__________________________________________________________________________
Product of Ex. 1
PVA 2 7.3
None
None
None ZO-20
ZO-10
ZO-14
ZO-20
ZO-9
ZO-2
1 7.4
" " " ZO-17
ZO-8
ZO-10
ZO-10
ZO-8
ZO-1
0.5 7.4
" " " ZO-15
ZO-5
ZO-8
ZO-5
ZO-5
0
0.1 7.4
" " " ZO-7
ZO-3
ZO-1
0 0 0
Acrylic
2 7.7
" " Gelled
ZO-24
ZO-9
ZO-10
ZO-19
ZO-7
ZO-1
1 7.9
" " None ZO-11
ZO-2
ZO-4
ZO-3
ZO-4
Tr
0.5 8.5
" " " ZO-5
Tr ZO-1
0 0 0
0.1 9.1
" " " 0 0 0 0 0 0
Oil 2 -- " " " -- -- -- ZO-4
ZO-3
ZO-2
Product of Ex. 2
PVA 2 7.3
None
None
None ZO-22
ZO-14
ZO-14
ZO-30
ZO-11
ZO-3
1 7.4
" " " ZO-18
ZO-8
ZO-14
ZO-10
ZO-8
ZO-2
0.5 7.4
" " " ZO-15
ZO-7
ZO-11
ZO-5
ZO-5
Tr
0.1 7.4
" " " ZO-7
ZO-4
ZO-5
Tr ZO-1
0
Acrylic
2 7.6
" " " ZO-20
ZO-9
ZO-13
ZO-21
ZO-9
ZO-3
1 7.8
" " " ZO-12
ZO-4
ZO-7
ZO-5
ZO-4
Tr
0.5 8.4
" " " ZO-7
ZO-2
ZO-1
Tr 0 0
0.1 9.1
" " " Tr 0 0 0 0 0
Oil 2 -- " " " -- -- -- ZO-7
ZO-5
ZO-3
Product of Ex. 3
PVA 2 6.8
None
None
Gelled
ZO-15
ZO-8
ZO-10
ZO-20
ZO-8
ZO-1
1 7.2
" " None ZO-15
ZO-9
ZO-9
ZO-14
ZO-5
Tr
0.5 7.3
" " " ZO-13
ZO-7
ZO-8
ZO-8
ZO-2
Tr
0.1 7.5
" " " ZO-6
ZO-2
Tr 0 0 0
Acrylic
2 7.3
" " " ZO-14
ZO-7
ZO-9
ZO-15
ZO-8
ZO-2
1 7.5
" " " ZO-11
ZO-5
ZO-8
ZO-8
ZO-3
0
0.5 8.1
" " " ZO-5
ZO-1
ZO-3
0 0 0
0.1 8.6
" " " Tr 0 0 0 0 0
Oil 2 -- " " " -- -- -- ZO-7
ZO-7
ZO-1
Comparative Examples
5-Hydroxymethyl-1-aza-
PVA 2 7.5
None
None
None ZO-3
ZO-4
ZO-1
ZO-4
ZO-2
0
3,7-dioxabicyclo
Acrylic
2 8.4
" " " ZO-11
ZO-3
ZO-4
ZO-6
0 0
(3.3.0)octane (51.2%
Oil 2 -- " " " -- -- -- 0 Tr 0
aqueous solution)
S-13 (Dow PVA 2 7.5
None
None
None ZO-13
0 0 ZO-14
ZO-19
ZO-12
Chemical Co.)
Acrylic
2 9.1
" " " ZO-13
0 0 ZO-20
ZO-11
ZO-5
Oil 2 -- " " " -- -- -- ZO-20
ZO-10
ZO-6
Bis(phenylmercuric)-
PVA 2 7.0
None
None
None ZO-19
ZO-11
ZO-9
ZO-13
ZO-10
ZO-15
dodecenyl succinate
Acrylic
2 9.0
" " " ZO-17
ZO-13
ZO-8
ZO-10
ZO-3
ZO-10
(Super Ad-it)
Oil 2 -- " " " -- -- -- ZO-17
ZO-6
ZO-14
(Tenneco Chemicals,
Inc.)
NOne PVA -- 7.5
None
None
None 0 0 0 0 0 0
Acrylic
-- 9.3
" " " 0 0 0 0 0 0
Oil -- -- " " " -- -- -- 0 0 0
__________________________________________________________________________
The superiority as biocides for surface-coating compositions of the polyoxymethyleneoxazolidines of this invention over a closely-related substituted oxazolidine is apparent from a comparison of the biocidal data for the products of Examples 1-3 with those for 5-hydroxymethyl-1-aza-3,7-dioxabicyclo(3.3.0)octane. The products of Examples 1 and 2, which are mixtures of substituted oxazolidines that contain the comparator 5-hydroxymethyl-1-aza-3,7-dioxabicyclo(3.3.0)octane as well as the 5-hydroxymethylpolyoxymethylene-1-aza-3,7-dioxabicyclo(3.3.0)octanes of this invention, were substantially more effective against bacteria and fungi than the comparator. Similarly, it is shown in the table that the product of Example 3 is more active at the 0.5% level in the PVA paint and at the 1% level in the acrylic paint than the comparator at the 2% level.
Each of the other bicyclic polyoxymethyleneoxazolidines disclosed herein can be used in a similar way to protect surface-coating compositions from attack by bacteria and fungi.
Claims (4)
1. A bicyclic polyoxymethyleneoxazolidine having the structural formula ##EQU4## wherein n represents a number in the range of 1 to 4.
2. A polyoxymethyleneoxazolidine as defined in claim 1 that is 5-[hydroxymethyl-di(oxymethylene)]-1-aza-3,7-dioxabicyclo(3.3.0)octane.
3. A polyoxymethyleneoxazolidine as defined in claim 1 that is 5-[hydroxymethyl-tri(oxymethylene)]-1-aza-3,7-dioxabicyclo(3.3.0)octane.
4. A polyoxymethyleneoxazolidine as defined in claim 1 that is 5-[hydroxymethyl-tetra(oxymethylene)]-1-aza-3,7-dioxabicyclo(3.3.0)octane.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/519,885 US3952000A (en) | 1974-03-04 | 1974-10-31 | Biocidal bicyclic polyoxymethyleneoxazolidines |
| US05/607,738 US4022906A (en) | 1974-10-31 | 1975-08-25 | Biocidal compositions containing bicyclic polyoxymethyleneoxazolidines |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US447797A US3890264A (en) | 1974-03-04 | 1974-03-04 | Surface-coating compositions containing polyoxymethyleneoxazolidines |
| US05/519,885 US3952000A (en) | 1974-03-04 | 1974-10-31 | Biocidal bicyclic polyoxymethyleneoxazolidines |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US447797A Division US3890264A (en) | 1974-02-15 | 1974-03-04 | Surface-coating compositions containing polyoxymethyleneoxazolidines |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US05/607,738 Division US4022906A (en) | 1974-10-31 | 1975-08-25 | Biocidal compositions containing bicyclic polyoxymethyleneoxazolidines |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3952000A true US3952000A (en) | 1976-04-20 |
Family
ID=27035097
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US05/519,885 Expired - Lifetime US3952000A (en) | 1974-03-04 | 1974-10-31 | Biocidal bicyclic polyoxymethyleneoxazolidines |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3952000A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3994916A (en) * | 1975-08-04 | 1976-11-30 | Imc Chemical Group, Inc. | Vinyl oxazolidines |
| FR2397452A1 (en) * | 1977-07-12 | 1979-02-09 | Tenneco Chem | PROCESS FOR INHIBITING THE DEVELOPMENT OF MICRO-ORGANISMS IN A FUNCTIONAL LIQUID BY ADDITION OF A POLYOXYMETHYLENE OXAZOLIDINE |
| FR2401206A1 (en) * | 1977-08-22 | 1979-03-23 | Tenneco Chem | DISPERSIONS OF PIGMENTS CONTAINING BIOCIDES OF THE POLYOXYMETHYLENE-OXAZOLIDINE TYPE |
| US4558114A (en) * | 1985-01-23 | 1985-12-10 | Ashland Oil, Inc. | Polymers derived from polyisocyanates, bicyclic amide acetals and oxazolines |
| US4562240A (en) * | 1984-12-20 | 1985-12-31 | Ashland Oil, Inc. | Bicyclic amide acetal/polyol/polyisocyanate polymers |
| US5370876A (en) * | 1993-01-08 | 1994-12-06 | Microbarriers | Antimicrobial protective skin composition and method for protecting skin from body fluids |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3738992A (en) * | 1972-02-07 | 1973-06-12 | Commercial Solvents Corp | 1-aza-5-hydroxymethyl-3,7-dioxabicyclo-(3.3.0)-octann |
| US3838164A (en) * | 1970-06-08 | 1974-09-24 | Sun Chemical Corp | Crosslinking monomers containing the 1-aza-3,7-dioxabicyclo(3.3.0)octane structure |
-
1974
- 1974-10-31 US US05/519,885 patent/US3952000A/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3838164A (en) * | 1970-06-08 | 1974-09-24 | Sun Chemical Corp | Crosslinking monomers containing the 1-aza-3,7-dioxabicyclo(3.3.0)octane structure |
| US3738992A (en) * | 1972-02-07 | 1973-06-12 | Commercial Solvents Corp | 1-aza-5-hydroxymethyl-3,7-dioxabicyclo-(3.3.0)-octann |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3994916A (en) * | 1975-08-04 | 1976-11-30 | Imc Chemical Group, Inc. | Vinyl oxazolidines |
| FR2397452A1 (en) * | 1977-07-12 | 1979-02-09 | Tenneco Chem | PROCESS FOR INHIBITING THE DEVELOPMENT OF MICRO-ORGANISMS IN A FUNCTIONAL LIQUID BY ADDITION OF A POLYOXYMETHYLENE OXAZOLIDINE |
| FR2401206A1 (en) * | 1977-08-22 | 1979-03-23 | Tenneco Chem | DISPERSIONS OF PIGMENTS CONTAINING BIOCIDES OF THE POLYOXYMETHYLENE-OXAZOLIDINE TYPE |
| US4562240A (en) * | 1984-12-20 | 1985-12-31 | Ashland Oil, Inc. | Bicyclic amide acetal/polyol/polyisocyanate polymers |
| US4558114A (en) * | 1985-01-23 | 1985-12-10 | Ashland Oil, Inc. | Polymers derived from polyisocyanates, bicyclic amide acetals and oxazolines |
| US5370876A (en) * | 1993-01-08 | 1994-12-06 | Microbarriers | Antimicrobial protective skin composition and method for protecting skin from body fluids |
| US5725875A (en) * | 1993-01-08 | 1998-03-10 | Microbarriers | Protective skin composition |
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